Methods for the rapid recovery of heavy water and other products



July 27, 1965 s. RUSKIN 3,197,402

METHODS FOR THE RAPID RECOVERY OF HEAVY WATER AND OTHER PRODUCTS Filed NOV. 20, 1957 INVENTOR. @M70/y fas/mf BY W K/ 4 ,PA/5y United States Patent O 3,197,402 METHDS FOR THE RAPID RECVERY F EEAVY WATER AND GTi-IER RGDUCIS Simon Lyon Ruskin, New York, NX.; Dan Ruskin, Milton Rader, and Carol Fax-hi, executors of said Simon L Ruskin, deceased Filed Nov. 20, 1957, Ser. No. 697,519 2 Caims. (Cl. 21d- 452) My invention relates to methods for the recovery of heavy water, primarily from sea water. It is known that sea water possesses a small but definite amount of heavy water also known as deuterium oxide, D20. Heavy water is a valuable article of commerce employed priman'ly in the operation of atomic reactors. Hitherto, recovery of heavy water'has been costly and very difiicult and attempts to form salts of D20 and concentration of the salts with ultimate separati-on of the D20 have been employed. This procedure, however, is not readily applicable to sea water already rich in various salts, or even to river or lake waters which are known as hard waters, due to their calcium or magnesium salts.

I have found that the separation of heavy water can readily be accomplished simultaneously with the separation of the dissolved salts whereby the heavy water can be concentrated to a commercially useful degree and simultaneously the salts present in sea Water are concentrated to a commercially useful amount. These concentrated salts may then be treated by processes commonly known to chemists for the separation of bromine, magnesium, calcium, sodium, gold and other minerals, and sulphates, chlorides and other salt radicals. The process of separation may be electrolytic, chemical, physical and combinations thereof as is well known in the art.

To accomplish my invention, I induce magneto hydrodynamic waves which separate the salts by altering the direction of the particles to the vector product of the magnetic field and the velocity. The sea water or other uid conducting system is allowed to flow under high velocity through a tube having as its core a permanent magnet, preferably an alnico magnet of the order of 10,000 gauss or more, where the length of the magnet bears to the diameter of the magnet a ratio of preferably 3 to l. Such are arranged in continuous series so that a series of poles are arranged as follows:

m KN m N s S NN s As the stream of water under pressure of 100 p.s.i. is forced through the pipe containing the permanent magnet core, the lines of force of the magnet are successively cut and the particles become diamagnetically charged and move at right angles towards the outer wall of the pipe. The magneto hydrodynamic effect produced, in addition to effecting a deposition of the salt particles along the walls of the pipe, also creates magneto hydrodynamic whirl rings whereby a circular motion is imparted to the outer layers of the concentrated salt solution. By introducing a progressive series of outlet tubes, emerging as branches from the main pipe, this concentrated salt solution is successively drained olf and the concentrated solution is accumulated in tanks by ordinary engineering procedures. Simultaneously, the main stream becomes progressively free from salts so that ultimately fresh Water is obtained in the main current flow. While this procedure provides a valuable method for the separation of salts and the production of fresh water, it is also highly ydesirable in many technical industrial uses such as the treatment of chemical effluent wastes, boiler water, laundry procedure, oil well flooding procedure for secondary oil recovery where a high degree of fresh water free from salts is desired. In cooling equipment `for atomic reactors this ICC method of separating salts from water permits the use of large quantities of sea water as well as pure water.

FIGURE 1 shows a coaxial pipe assembly 1 having a series of annular draw-off zones 2 and draw-olf headers 3 with pipes 4 interconnecting the:zones 2 and headers 3. A pump 5 circulatesthe liquid through the pipe assembly 1, and is gauged for'pressure at 7 and valved at 3, 9, and 10. The valves admit fresh liquid and expel utlized liquid when desired.

FIGURE 2 is a detail section of the pipe assembly 1, showing additionally the internal series magnets 11.

FIGURE 3 is an end section showing the manner in which the magnets are centrally supported by Webs 12 and cylinder 13. The liquid treatment passage is indicated at 14.

This valuable application of magneto-hydrodynamic waves arises when an electrically conducting medium is present in a magnetic field. Any hydrodynamic motion will give rise to induced electric felds'which produce electric currents. Becaus'etof the magnetic fields, these currents will produce forces which change the state of motion, thus producing a type `of wave motion called magneto hydrodynamic waves. A body moving -in a magnetic field becomes electrically polarized in a direction at right angles to the magnetic field and to the direction of motion. `The electric field thus produced is proportional to the vector product of the magnetic field and the velocity where H0 represents the strength of a homogeneous magnetic field.

An electric current, I, in a magnetic eld is acted upon by a force, F, which is at right angles to the -current and to the magnetic field The induced current system tends to transfer the central movement to the surrounding layers'.

In etlect, it may be said that I am producing a mechanical equivalent of a master and imparting to the salt particles considerably amplified force.

Yet another aspect of my invention is that by my procedure suspended particles present in my conducting fluid are thrown with such force against the containing walls that they are shattered and broken into smallest particles more eiectively than a colloid mill and my procedure can be used for milling purposes. By the same procedure I may improve such processes as powder metallurgy, powder welding, electroplating, chemical plating, paint dispersions, pigment suspensions, cold ultrasonic welding, high quality electrical cores, preparation of metallic components for the addition to glass for hardening, electrodes, metal catalysts, finely subdivided metallic fuels, high speed filtration and the like.

Yet another object of my invention is the separation of heavy water present in small quantities in sea water. I laccomplish this by taking advantage of the magneto hydrodynamic wavesVi-nduced in a conducting lluid of different density. Here the conditions prevailing for gases are closer to the conditions necessary for the separation of `heavy water.

I may also use my system of magneto hydrodynamic waves in the gas state for the separation of deuterium from hydrogen in the refinement of hydrogen, or I may promote deuterium exchange between hydrogen sulfide and water whereby deuterium sulfide concentrates in the magneto hydrodynamic whirl and is readily drained off in concentrated form. I may alsoV promote the concentration of heavy .water directly in the rst stages of concentration by inducing magneto hydrodynamic waves whereby the lighter hydrogen water enters the magneto hydrodynamic whirl at the circumference of the pipe,

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While the central main stream carried the higher concentration of heavy water. Since ions such as Mn, Fe, Co, Ni and Cu as well `as the rare earths are paramagnetic and may reverse the reaction, it is desirable to check the outovv to determine whether the magneto hydrodynamic ywhirl has carried o the heavy Water or whether the main trunk flow is the enriched heavy water. By recycling three to live times under high pressure, increased concentratiori is attained. By these procedures a 1000 fold increase of concentration of heavy .water is obtained and current procedures such as dual temperature exchange is avoided. To obtain high water pressure,A natural pressure heads. may be used such as the tide elevation at the'Bay of Fundy or water falls. Recycling may be conducted by supplementary pressure pumps. Recycling procedures may follow conventional means for that purpose.

' Yet 'another object of my invention is the enhancement of -chemicalreactivity by altering crystal symmetry of solids. Syrnmetrical crystals are generally at -base energy levels and Iin the moist stable state, whereas antisymmetrical states are in general heavier and more reactive Thus catalytic solids may 'be made more catailytic and chemical reactions that ordinarily need active catalysts may proceed -vvith little or no catalyst. T-hus organometal compounds form more readily when the metallic oxide or -sulde has been separated by magneto hydrodynamics waves. Thus in the preparation of tetraethyl lead, I may use such inactive lead compounds such as lead suldeglead oxide or lead dioxide, suspended in water and separated by magneto hydrodynamics waves. These compounds now react readily with ethyl chloride to form tetraethyl lead with the avoidance of the forming of a sodium-lead allo-y. Thus also the reactionor" lithium ethyl or sodium ethyl with lead sulfide at room temperature produces a rapid reaction with high yields.

Similarly I may use magneto hydrodynamic waves in the rapid separation of mined ores. The ore is ground to flotation size and suspended in water. It is then subjected to magneto hydrodynamic =waves and collected through the magneto hydrodynamic Whirl at the circumference of the pipe. The ore particles are shattered to fragments of 2 microns which -are readily leached and concentrated. Thus in lthe extraction of uranium from ores, one may use low grade U3O8 0.183% ore and leach directly -with sulfuric acid from the Whirl outlets along the circumference of the pipe.

Yet another object of my invention is the concentration of free (organic) radicals in solution. Thus I may use a diamagnetic solution for the conversion of parahydrogen. Thus triphenylmethyl will readily convert parahyd-rogen which may be collected from the magneto hydrodynamic whirl. I may vfor this purpose also employ tetraphenyldiphenoquinodimethane and stilbenoquinodimethane, both of which are diamagnetic. Similarly, rubrene and dibenzanthracine may be employed.

Still another aspect of my linvention is the promotion of hydroforming of petroleum and free radical formation in petroleum gases leading to the formation of gasoline. Thus petroleum gases or liquid subjected to magneto hydrodynamic Vwaves react to for-m long chain hydrocarbons, isomerize, form alkyl and alkane compounds.

While I conduct my magneto hydrodynamic procedure at C. to 25 C., I may also go to low temperatures and even to 273 C. in gases. Active charcoal is best treated at low temperatures. Thus it became readily possible to separate ortho from para hydrogen Without resorting to the low temperature of -271 C. Since parahydrogen is diamagnetic and ortho hydrogen is paramagnetic, the parahydrogen is repelled at right angles when passing through the tube containing the alnico magnet while the ortho hydrogen passes parallel to the permanent magnet to be collected at the outlet. Likewise, the same occurs` with deuterium and separation is attained.

In the case of deuterium, We also have para and ortho forms with a para-ortho ratio of 2:1 with the ortho `form diamagnetic so that the ortho fr'orm of deuterium oxide may be repelled from Ithe alnico magnet along Nwith the para form of :light water. Equilibrium of light hydrogen may readily be catalyzed .by hydrogenation catalysts such as platinum, nickel and iron. Active charcoal will do so at 10W temperatures. Paramagnetic substances like atomic hydrogen, free organic radicals, nitric oxide, nitrogen dioxide, all of which are paramagnetic on account of their unpaired electrons, also oxygen, which Vis paramagnetic, and paramagnetic ions in solution such as Mn, Fe, Co, Ni and copper, promote equilibrium.

Where a diamagnetic outer tube is desired, I may use a zinc pipe.

Example I Inside the center of a 20 foot stainless steelpipe, is placed a continuous series of alnico magnets each 6%. inches in diameter and 20 inches long. At each 1/2 yfoot distance is a circumferential drain leading into a common tank. The liow of sea water through the main pipe trunk returns for recirculation and valves are arranged so as to allow drainage ofthe main trunk at every third circulation. The sea Water enters the pipe at 100 p.s.i. and is kept circulating at maximum speeds under 100 p.s.i. The contents of the main lilow is now gassed with HZS to allow deuteriurn exchange While running through a hot tower at 100 C. Thus suliide and accompanying `water are run through a heat exchanger and a cold tower at 25 C. reversing the equilibrium and causing the water to be enriched by the high deuterium sulde. Additional cycles allow the enriched water to be raised to a D20 concentrati-on lthat is` distilled.

The salts accumulated from the magneto hydrodynamic whirl are concentrated by evaporation or electrolytically separated as desired.

Example II A ton of uranium ore containing L0.183% USOS is ground to iiotation size and added to 6 tons of Water. The slurry is pumped through the pipe as described in Example I under 100 p.s.i. and recycled three times. The solids collected from the magneto hydrodynamic whirl are led into a tank of sulfuric acid and leached. Processing of the uranium proceeds from the leaching in customary manner.

Example III 100 lbs. of lead sulfide is suspended in a ton of water. The slurry is pumped through the pipe described in Example I, under 200 p.s.i. and recycled iive times. The solids are collected from the magneto hydrodynamic whirl and dried in vacuo. The lead sulfide reacts in l5 to 2O minutes with lithium ethyl to form lead tetraethyl. The yields are approximately to 90%.

Yet another aspect of my invention is the addition to the heavy water obtained, small amounts of rhenium powder or colloidal rhenium to prevent the loss of heavy water when in use in the atomic reactor. At super stream temperatures some ionization of the heavy Water occurs leading to the formation of H2O2 and H and O. The rhenium catalyzes the breakdown of the H2O2 and recouverts to Water the hydrogen and oxygen.

' Example IV To 500 gallons of heavy water used in an atomic reactoris added 200 grams of rhenium powder. The whole is allowed to circulate continuously for the modification of the reactor energy.

What I claim is:

l. The proceess of enriching the content of heavy Water in water of ordinary heavy water content comprising the steps of passing the ordinary water through an elongated path in a strong magnetic iield essentially perpendicular to the fluid flow so as to cause the more cornrnon para form of light Water and the less common ortho form of heavy water to be propelled outward from the main stream to the periphery of the liquid to form a light Water enriched layer, collecting said light water enriched layer from said periphery as Waste, and collecting said heavy Water enriched molecules from the main stream iol` further utilization.

2. The process of separating a heavy water enriched component from ordinary Water which contains a large amount of light water and a small amount of heavy Water, said light Water having a large fraction thereof composed of diamagnetic light Water molecules with a small fraction thereof composed of paramagnetic light water molecules, and said heavy water having a small fraction thereof composed of diamagnetic heavy water molecules with a large fraction thereof composed of pararnagnetic heavy Water portion, the resultant process comprising continually passing said ordinary Water along an elongated path in a strong magnetic field of at least 10,000 gauss essentially perpendicular to the uid flow, allowing said magnetic eld to propel all diamagnetic Water molecules outward from the main stream to the periphery of the liquid While leaving all paramagnetic Water molecules unaiected, said all diamagnetic Water molecules including a decreased proportion of heavy Water molecules by virtue of the fact that heavy Water has said small fraction of diamagnetic molecules while said light Water has said large fraction of diamagnetic molecules, said unaffected pararnagnetic molecules being enriched in heavy Water molecules by virtue of the fact that heavy Water has said large fraction of paramagnetic molecules While said light Water has said small fraction of paramagnetic molecules, continually collecting said decreased heavy Water proportion diarnagnetic molecules romvsaid periphery as waste, and continually collecting said heavy water enriched paramagnetic molecules from the main stream for further utilization.

References Cited by the Examiner UNITED STATES PATENTS 531,183 12/94 Harris 210-42 2,099,593 11/37 Bender et al. 210--223 2,352,791 7/44 Kmmholtz 204-155 2,609,150 9/52 Bludeau 241-15 2,636,608 4/53 Prevost 210--222 2,652,925 9/53 Vermeiren 210-223 2,684,329 7/54 Rony 204-155 2,743,225 4/56 Ohlinger et al. 204-l54.2 2,764,359 9/56 Szeguari 241--15 2,770,591 11/ 56 Wigner et al. 204-154.2 2,798,611 7/57 Prevost 210-222 2,825,464 3/58 Mach 210-222 2,951,586 9/60 Moriya 210-223 OTHER REFERENCES Ellis: Fresh Water from the Ocean published by Ronald Press Co., N.Y. (1954), pages 61-67 relied upon.

Eliassen et al.: Journal American Water Works Association, October 1958, pages 1371-1385 relied upon.

MORRIS O. WOLK, Primary Examiner.

ROGER L. CAMPBELL, CARL F. KRAFFT, DELBERT E. GANTZ, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,197,402

Simon Lyon Ruskin July 27, 1965 It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column Z, line 40, for "master" read maser Signed and sealed this 8th day of February 1966u (SEAL) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. THE PROCESS OF ENRICHING THE CONTENT OF HEAVY WATER IN WATER OF ORDINARY HEAVY WATER CONTENT COMPRISING THE STEPS OF PASSING THE ORDINARY WATER THROUGH AN ELONGATED PATH IN A STRONG MAGNETIC FIELD ESSENTIALLY PERPENDICULAR TO THE FLUID FLOW SO AS TO CAUSE THE MORE COMMON PARA FORM OF LIGH WATER AND THE LESS COMMON ORTHO FORM OF HEAVY WATER TO BE PROPELLED OUTWARD FROM THE MAIN STREAM TO THE PERIPHERY OF THE LIUQID TO FORM A LIGHT WATER ENRICHED LAYER, COLLECTING SAID LIGHT WATER ENRICHED LAYER FROM SAID PERIPHERY AS WASTE, AND COLLECTING SAID HEAVY WATER ENRICHED MOLECULES FROM THE MAIN STREAM FOR FURTHER UTILIZATION. 